N-substituted x



Patented Sept. 23,

N-SUBSTITUTED 4,6-DIAMINO METANILIC ACIDS AND THE CORRESPONDING NITRO DERIVATIVES Robert C. Gunther, Easton, Pa., assignor to General Aniline & Film Corporation, New York,; N. Y., a corporation of Delaware No'Diawing. Application October 29, 1949,

' Serial No. 124,501

Claims. (01. 260-509) The present invention relates to N-substituted 4,6-diaminometanilic acids in which the amino group in the 4- position is substituted by hydroxy alkyl and to thenitro intermediates from which said metanilic acid compounds. are derived.

In the copending application, Serial No. 640,382, filed on January 10, 1946, by Willy A.Schmidt and Vsevolod Tulagin, now United States Patent No. 2,486,440, there is. described the production of azine dye images by color .formingdevelop ment while utilizing inter alia as the .color developer derivatives of zn-diamino-ani-linel While these color developers have been found to be effective in producing the desired dyestuff images in the presence of the usual color forming components, it is notedthat they. have a tendency to be adsorbed to silver halide grains o'ithe photographic emulsions, thereby making it: difiicult to effect the complete, removal thereof from the emulsion by washing after development. Furthermore, said compounds have been observed to cause stain in the reduction pof silver halides, particularly when such reduction takes place in the absence of a color former.

Difiiculties have also been encountered inxthe production of yellow dye images by the utilization of the aforestated developers. Experience has shown that when using such developers with color formers generally employed for the production of yellow azomethine images, i. e., open chain keto methylene compounds, magenta images rather than yellow images ensue. These magenta images may be subseduentlyconverted into yellow images but only by a separate step involving a treatment with an alkali. I i

It has now been discovered that the production of azine dye images can be effectively carried out without the aforenoted objections ii there .be employed as color developers derivatives of 4,6 diamino metanilie acid in which the amino group in the 4-position is substituted by a hydroxyalkyl group. Inasmuch as said compounds are capable of effecting the reduction of silver halides including latent images without the formation of stain, they may also be employed as developers for black and white images. a a p a These developers also have theunique property of yielding yellow dyeimages directly when employed to develop a developable silver halide emulsion in the presence of an'open chain keto methylene compound. They are therefore ad-' mirably'suited for the production infone development step of azine dye images in'the three subtractive colors.

Said metanilic acid derivatives and the nitro intermediates from which they are derived are novel compounds. The nitrointermediates are per se yellow dyestuffs having excellent affinity for W001 and nylon.

Such metanilic acid derivatives and the nitro compounds serving as intermediates for their production and as new dyestuffs constitute the purposes and objects-of the present invention.

The new compounds contemplated herein are typified by the following structural formula;

such as phenyl, toluyl, carb'oziymethylphenyl, carboxyethylphenyl, carboiiym'ethoxyphenyl," carboxyethoxyphenyl, hydroxymethylphenyl, hydroxyethylphenyl, hydroxymethoxyphenyl, hy-

droxyethoxyphenyl, and the like, R; is hydroxyalkyl, and R3 is nitro or primary amino.

Examples of compounds illustrative of those within the general formula are the following:

NHz

4-(B-hydroxyetl1ylamino) 6-(4-carboxy-methoxy phenylamino) metanilic acid and the corresponding nitro compound NH ws HOsS NHCH2OH 4 (liydroxymetl1ylamin'ol 6 (4"-me tho;zy p heny1ainino)- metanilic acid and the corresponding nitro compound 4,6-di(B-hydroxyethylamino)-metanilic acid and the corresponding nitro compound NECH2CH2OH 4-(fi-liydroxyethylamino)-6-plienylamlno-metanl1ic acid and the corresponding nitro compound 5. If'H-CHzCHgSOaH HOsS i NHCH2CH2OH 4- (B-hydroxyethylarhino -6-(B-sulfoethylamino) -metani1ic V aci d and the corresponding nitro compound NHCHPCHOH 4- (B-hydroxy-B-methyl-ethylamlno) -6-phenylamindmetanilic acid and the corresponding nitro compound 4- (o-dl- [h ydroxymethyl] -ethylamino) -6- (3 -ethoxy phenylamino)-metani1ic acid and the corresponding nitro compound 8. IITHCH:

4-(fl-hydroxy ethylamino)-6-methylamino-metanllic acid and the corresponding nitro compound ITHCHsOH l lHs 4- (hydroxymethylamino -6- (methyl phenylamino) -meta nilic acid and the corresponding nitro compound 1% CHI)! NHC4Ha OH 1 m,

4- d-hydroxybutylamino) -8dimethylamino-metanilic a and the corresponding'nitro compound cid 11. NHCHzC o 011 -Ni1omosnoi1 4- (B-hydroxyethylamino) -6-carboxymetliylamino-metanll1c acid and the corresponding nitro compound n-cmooon NHCHzCHzOH 4- (B-hydroxyethylamino) 6- N-phenyl-N-carboxymethyl) amino metaniiic acid and the corresponding nltro com- DOlllId V p D V The aforementioned compounds are prepared by reacting in the'proper sequence 2,4-dichlor'o- 5-nitrobenzene sodium sulfonate with the amines desired to be introduced into the 2- and 4- positions of the benzene ring, and theneffecting reduction of the nitro group. to an amino group.

The preparation ofithe compound by the aforesaid method is made possible by the fact that the chlorine. atom inthe l-position is more easily replaced by an' amino group than the chlorine atom in 2-position.. .Thus by refluxing jthe 2,4-dichloro-5-nitrobenzene sodium sulfonate with an equivalent off an amine, the: chlorine atom in l-position is selectively replaced by such amine. By subsequently treating the resulting compound with the'same or a different amine under more elevated temperatures, i. a, temperature ranging from to C., the chlorine atom in '2-position in replaced by the amine.

'The following examples will serve to illustrate the invention but it isto be understood that the invention is not restricted thereto. The parts are by weight unless otherwise stated.

Example 1 'Into a l-liter, 3-necked round-bottom flask equipped with a mechanical stirrer and a reflux condenser was placed 147 parts of the sodium salt of 2,4dichloro-5-nitrobenzene sulfonic acid, 31 parts of ethanolamineand 54 parts of sodium carbonate dissolved in 250 parts of water. After the stirrer was started, the contents of the flask were gently refluxed for l o'hours. 2 i0 parts of 30% sodium chloride solutionwere added to the hot reaction mixture and the flask was then cooled in an ice bath. Theprecipitated orange solid was collected by filtration,washed with a small; amount of water, and d ried overnight at 80-90'C I -v I A glass interliner for an Aminco'shaking type bomb was charged with 95.6 parts of the 2 chloro 4 (5 hydroxyethylainino) :5-nitrobenzene sodium sulfonate (prepared as above). 30 parts of aniline and 3,4 parts of sodium carbon'ate dissolved in 200 parts oi water. The liner was sealed in the bomband the bomb shaken at M0 0. for 15 hours, The bomb was, cooled and the solid removed from the interliner with small amounts of hot water. 300 parts oi.30% sodium chloride solution were added with'vigorous. stirring of the mixture and the whole, was then cooled in an ice bath for several hours. The presprings cipitated solid was collected by filtration,- washed with 50 parts of water, and then digested with 200 parts of ethanol; The product was again collected on a filter and dried overnight at 60C. in a vacuum oven.

parts of 2-phenylamino-4-(B-hydroxyethylamino),-5-nitrobenzene sulfonic acid (prepared as above) were added portion-wise to a boiling solution of parts of sodium hydrosulfite in 222 parts of 10% sodium hydroxide. After reduction is complete, a small amount of decolorizing carbon is added to the solution. The mixture is boiled vigorously for several minutes and then filtered rapidly through a fluted filter. The compound was then isolated from the'clear filtrate as the inner salt by acidification with glacial acetic acid.v 'Themixture was cooled in an ice bath 'for several hours, the inner salt collected on a'zfilter and washed with water.. The product was then dried six hours at 65 C..in'a vacuum oven and constituted the 4 (p hydroxyethylamino) -6- phenylamino-metanilic acid.

Example II The procedure is thesame as in Example I excepting that the aniline is replaced by 56 parts of p-amino phenoxy acetic acid.

The product produced is 4-(B-hydroxyethylamino) -6- (4'-carboxy-methoxy phenylamino) metanilic acid.

Example III The proces is the same as in Example I excepting that the aniline is replaced by 20 parts of ethanolamine.

The product obtained is 4,6-di-(fl-hydroxyethylamino) -metanilic acid.

Example V The procedure is the same as in Example I excepting that the aniline is replaced by 42 parts of taurine.

The product obtained is 4-(p-hydroxyethylamino) -6- (e-sulfo-ethylamino) -metanilic acid.

Example VI The procedure is the same as in Example I excepting that the ethanolamine is replaced by 38 parts of isopropanolamine.

The" product obtained is 4-(B-hydroxy- 3- methylethylamino) 6 phenylamino metanilic acid.

Example VII The procedure is the same as in Example I excepting that the ethanolamine is replaced by 53 parts of 2-amino-2-methyl propane diol (1.3), and the aniline by 46 parts of m-methoxy aniline.

The product obtained is 4-a-di-(hydroxymethyl) ethylamino 6 (3 ethoxy phenylamino) -metanilic acid.

Example VIII The procedure is the same as in Example I excepting that the aniline is replaced by 10 parts of methylamine.

The product obtained is 4-(p-hydroxyethylamino) -6-methylamino metanilic acid.

Exam'pZeJIX' The procedureis the same as in Example I excepting that the-ethanolamine is replaced by 24 parts of methanolamine and the aniline, by 36 parts ofN-methyl aniline.

The product obtained. is 4-(hydroxymethylaminol-fi (methylphenylamino) -metanilic acid.

Example X The procedure is the same as in Example, I excepting that the aniline is replaced by 50 parts of N-phenylamino acetic acid.

The product obtained. is 4-(fi-hydroxyethylamino) -6-(N phenyl-N-carboxymethylamino) metanilic acid.

As stated, the aforementioned metanilic acid derivatives are characterized by their marked ability to effect reduction of silver halides, i. e., latent images, reverse images, bleached images, andthelike, without formation of objectionable stain. As a consequence :of thereducingpower they may be employed for. development of black and white images or for the productionoi color im ges.

One of the most notable properties of the afore mentioned metanilic acid derivatives, however, is their ability to directly yield yellow dye images. This result is achieved when employing the developers to develop a developable silver halide emulsion in the presence of an open chain keto methylene compound even though the emulsion during a subsequent processing step be treated with an acidic bleach bath as is usual in the processing of film to azine dye images. In other words, whereas the formerly employed, 2,4-diamino anilines only yielded yellow images, as the result of a subsequent alkaline treatment, the developers contemplated herein yield such images directly and without such subsequent processing with an alkaline bath. As a consequence such developers very materially contribute to the utilization on a commercial scale of the azine method for processing film in the three subtractive colors.

The yellow dyes obtained by color development with my developers appear to be true azines. Thus they withstand treatment with an acid bisulfite whereas yellow azomethines do not. Furthermore they are not split by strong mineral acids as happens with the yellow azomethines. Such yellow dye images have excellent lightfastness and brilliance and they adequately complement the magenta and cyan dyes produced by the azine methods.

The color formers employed for producing the dye images are those used in the production of color developed images, i. e., those containing aromatic-primary amino, phenolic hydroxyl or active methylene groups.

The nitro intermediates from which the metanilic acid derivatives are produced are novel yellow dyestuifs having a high affinity for W001 and nylon.

Where used herein, the term the corresponding nitro compound is intended to mean the nitro derivative from which the metanilic acid is produced by reductionof the nitro group.

The present application is a continuation-inpart of my application Serial No. 793,532, filed December 23, 1947, now abandoned, entitled Color Developers for the Production of Phenazonium Dyestuff Images, and my application Serial No. 101,913, filed January 28, 1949, and entitled Color Developers for the Production of 7 Azine images," is now U. S. Patent 2,570,116, issued October 2, 1951.

Attention-is directed to the later filed case for examples of the use of the metanilic acid derivatives in the production of azine dye images.

Various modifications of the invention will occur to persons skilled-in this art, and I therefore do not intend to be limited in the patent granted except as necessitated by the appended claims.

I claim:

1. Compounds of the following structural formula: V V t wherein R is a member selected from the class consisting of hydrogen and lower alkyl radicals, R1 is a member selected from the class consisting of lower acyclic aliphatic radicals and a monocyclic carbocyclio aromatic radical, R2 is hydroxy lower alkyl, and R3 is a member selected from the class consisting of nitro and primary amino.

2. 4 (pV-hydroxyethylamino)-6-phenylaminoe metanilic acid. .7 i

' 3. 4 (18 hydroxy ,8 methylethylamino) 6- phenylamino metanilic acid. 7

4. 4 (,6 hydroxyethylamino) -6 methylamino metanilic acid v 5. 4 :(hydroxymethylamino) -6-(methy1phenylamino) emetanilic acid,

i ROBERT C. GUNTHER.

' REFERENCES CITED.

The following references are of record in the file of this patent:- 1 Y N T emsa t P T OTHER REFERENCES Beilstein, vol. XIV, p. 719. 

1. COMPOUNDS OF THE FOLLOWING STRUCTURAL FORMULA: 